A Chemoselective α-Oxytriflation Enables the Direct Asymmetric Arylation of Amides

Summary Until recently, the direct oxidative oxysulfonylation of carbonyl compounds was limited to ketones. Here, we report the first direct oxytriflation of simple, non-activated amides. Amide umpolung with triflic anhydride and pyridine- N -oxide in the absence of external nucleophiles directly leads to the formation of reactive α-triflates in a single step, which provides a platform for the deployment of valuable downstream α-functionalization reactions. The utility of this method was demonstrated by in situ clean conversion to their corresponding bromides, as desirable starting materials for nickel-catalyzed deracemizing enantioselective arylation. This approach not only enables a telescoped asymmetric arylation of unsubstituted amides but also extends its scope because of the broad chemoselectivity and functional group tolerance of the method.